The analyses of alkyllead compounds in fish and environmental samples in Ontario,Canada (1981–1987)

Analyses of fish and other environmental samples (clams, macrophytes, sediments and waters) from areas upstream and downstream from two alkyllead manufactures beside the St Lawrence and St Clair Rivers, Ontario, show a clear indication of elevated alkyllead levels in samples near the industries. Most species of fish contained alkyllead compounds with tetraethyllead and triethyllead as the predominant forms. Most fish from the contaminated areas contained 50–75% of total lead as alkylleads. Carp, yellow perch and white sucker were generally the most contaminated species while pike, alewife and rock bass were the least contaminated. Average alkyllead levels varied from year to year but declined steadily after 1981. For example, the geometric mean of alkyllead compounds in carp from the St Lawrence River decreased from 4207 μg kg^?1 in 1981 to 2000 μg kg^?1 in 1982 and to 49 μg kg^?1 in 1987, reflecting the reduction of alkylleads in the effluents and the closure of one of the manufactures in 1985. Alkyllead levels were consistently lower in muscle and carcass samples in comparison with whole fish containing fatty intestines. However, muscle levels were generally equal to carcass levels. The concentrations of alkyllead compounds were generally low in clams, macrophytes, sediments and waters except from the immediate vicinity of the manufactures' final effluent discharges.     

The determination of tetra-alkyllead and ionic alkyllead compounds in seafood

Extraction methodologies were developed for tetra-alkyllead and ionic alkyllead compounds in seafood. Tetra-alkylleads were extracted with n-hexane after the samples had been enzymatically hydrolyzed. The ionic alkylleads were complexed with diphenylthiocarbazone (dithizone) at pH 8 and 9 from enzymatically hydrolyzed samples to optimize recovery. The dithizone extracts were butylated prior to analysis by gas chromatography–atomic absorption spectrometry (GC AA). Instrumental detection limits ranged between 1.6 and 2.3 pg lead. Application to a limited number of seafood samples indicated the possible presence of trace amounts (ca 1 ng g^?1) of trimethyllead in some samples. No other alkylleads were detected.     

Speciation of alkyllead compounds by GC-AAS: A state of affairs

A synopsis of the organolead studies performed at our University is given. The different environmental applications such as air, wet atmospheric deposition and dust are summarized and the analytical characteristics of the extraction/derivatization/gas chromatography—atomic absorption spectrometry methodology for the species specific determination of ionic alkyllead species are described.     

Activated carbon as adsorbent for alkyllead in air

A method is described for the determination of alkyllead in air with activated carbon as adsorbent. The main factor affecting the adsorption capacity of the activated carbon for alkyllead was the concentration of hydrocarbons in the sampled air, as these were also adsorbed. Particulate inorganic lead was collected on a membrane filter in front of the adsorbent. The alkyllead was extracted from the adsorbent into hot nitric acid, and the concentration determined by electrothermal atomic absorption spectrometry. The detection limit was 0.002 μg Pb m^?3 (sample volume 1 m³), and precision was 9.5% r.s.d. at 2.1 μg Pb m^?3 alkyllead. The method was used to monitor exposure of gasoline tank truck drivers to alkyllead. During the filling of tank trucks with leaded gasoline, alkyllead concentrations from 1 to 750 μg Pb m^?3 were found in the drivers' breathing zone, but most were well below the Norwegian TLV of 75 μg Pb m^?3.     

Separation of dissolved alkyllead and inorganic lead species by coprecipitation with barium sulphate

Coprecipitation with barium sulphate is shown to be an efficient and convenient method of preventing the interference of relatively large amounts of inorganic lead in the determination of alkyllead species by differential-pulse anodic stripping voltammetry. The coprecipitation method has several advantages over complexation of lead with EDTA; ionic alkyllead can be measured in solutions of low pH (pH < 2), or at deposition potentials more negative than ?1.0 V.     

Environmental sources and sinks of alkyllead compounds

Evidence is presented in favour of a natural environmental alkylation process as a source of atmospheric vapour-phase alkyllead. Several species of marine flora have been cultured under laboratory conditions with added doses of inorganic lead, and production of alkyllead, predominantly trimethyllead (Me₃Pb⁺), has been measured. Atmospheric concentrations and ratios of alkyl and inorganic lead at urban, rural and remote sites suggest that differential decay and deposition processes for different species, together with an environmental alkylation source, may explain enhanced ratios of total alkyllead/total lead in maritime air masses.     

Determination of organolead compounds and of chromate beside Cr(III)

A procedure for the preconcentration and determination of ionic alkyllead compounds in surface waters and human urine and tetraalkyllead compounds in ambient air is described.Concentration ranges are given and difficulties arising in the validation of TriML and DiML in some matrices are discussed.A chromium(VI) speciation procedure consisting of a selective biosampling step by using human erythrocytes and two subsequent determination methods (GFAAS and reverse-FIA) is introduced.     

The effects of organolead compounds on a freshwater and a marine alga

There are conflicting reports concerning the toxicity of tetraalkyllead (TAL) compounds to algae. A number of groups have found the TAL's to be comparable in toxicity with the trialkyllead compounds (R₃Pb⁺), whereas in a recent report it is suggested that the TAL's themselves are completely non-toxic and any apparent toxicity is due to R₃Pb⁺ breakdown products. With the object of identifying the toxic agent, the effect of Et₄Pb (TEL) on two algal species was re-examined. Analyses were carried out during the course of the incubations to establish the nature and concentrations of organoleads present in both media and algae, and hence evaluate their relative contributions to total toxicity. Algae were also cultured in the presence of Me₄Pb (TML), Me₃PbCl, Et₃PbCl, Bu₃PbCl and Et₂PbCl₂ to assess relationships between alkyl chain length and degree of substitution around the lead on algal activity. Additions of selenide and sulphide were made to the Et₃Pb⁺ and Et₂Pb²⁺ systems to see if these environmentally abundant species reduced or enhanced organolead toxicity. Problems were encountered in the analysis of the heterogeneous TEL containing media. Regardless of the analytical problems, the results confirm the previous findings that TAL's are non-toxic to algae and it is the R₃Pb⁺ breakdown products which are responsible for the apparent toxicity of the TAL's. The trialkylleads were the most toxic of the several alkyllead species studied, and within the trialkyl series toxicity increased with alkyl chain length. Neither selenide or sulphide had any significant ameliorative effect on alkyllead toxicity. It was found that the ionic organoleads were complexed on the TAL's and this complexing led to a number of unexpected results.     

Sensitive detection of ionic organolead compounds by coupling hydride generation (HG) with transversely heated graphite atomizer-atomic absorption spectrometry (THGA-AAS)

The detection of ionic alkyllead compounds using the coupling of flow injection analysis system-hydride generation (FIAS-HG) with transversely heated graphite atomizer atomic absorption spectrometry (THGA-AAS) has been worked out. Very low limits of detection can be achieved if the hydride products are enriched in the graphite furnace. Under optimised conditions (concentration of sodium borohydride, hydrogen peroxide and acidity as well as the furnace temperature) calibrations are carried out in the range of 0.1 to 5 μg/L. With a 1.5 mL sample loop, the limit of detection is calculated to be about 7 ng/L, but it can be lowered to below 1 ng/L if larger sample volumes are used for the enrichment.     

Bioaccumulation of alkyllead compounds from water and from contaminated sediments by mussels

The bioconcentration of alkyllead compounds from water and from contaminated sediments by freshwater mussels (Elliptio complanata) has been investigated. Higher levels of trimethyllead than triethyllead species are accumulated for the same exposure period. In-vivo transformation of the trialkyllead species by a series of dealkylation reactions giving dialkyllead and inorganic lead(II) species appears to take place. Rates of accumulation are higher for the more contaminated sediments.     

Ionic alkylleads in avian tissues from aquatic and terrestrial environments

Ionic alkyllead concentrations in soft tissues of pigeons from urban Montreal and environs were appreciably different from the variety and concentrations of alkyllead analytes which characterized mallard ducks culled from a sanctuary in eastern Ontario. The major toxicant in pigeons, triethyllead (Et₃Pb⁺) reflected the exclusive use of tetraethyllead as a gasoline additive in both regions. Urban colonies of pigeons were characterized by significantly greater concentrations of Et₃Pb⁺ than were specimens from a suburban/rural colony. In contrast, the major toxicant in ducks was trimethyllead although six other alkyllead analytes were also observed. An environmentally mediated methylation of Pb²⁺ which is more active in (but not restricted to) aquatic environments is postulated to account for the ubiquity of trimethyllead in ducks.     

Transmethylation of metals in aquatic systems

Transmethylation reactions between organometals and metal ions in aqueous solutions in biotic and abiotic systems, with and without the presence of sediment, were investigated. It was found that alkyllead compounds can transfer their alkyl groups to Sn(II) and Sn(IV) ions to form various methyltin compounds in biotic and abiotic systems. The presence of sediment enhanced the transmethylation reactions. Methyltin compounds do not transfer their methyl groups of Pb(II). Methylarsenic acids transfer their methyl groups to Sn(II) and Sn(IV) in an abiotic system, but not in a biotic system containing sediment. The strong adsorption of tin onto sediment was the reason for the non-availability of tin ions for methylation. Methylarsenic acids do not transmethylate Pb(II). Other alkyllead compounds, such as ethyllead and butyllead species were also able to transfer their alkyl groups to tin. When both trimethyllead and triethyllead species are present in the same system, only the individual monoalkyl tin species were formed in both the Sn(II) and Sn(IV) solutions. No mixed alkyltin was produced. The findings of this study suggest that alkyllead compounds, if present in the environment, could be potential methylating agents for the formation of other methylmetals, such as methyltins. Methyltin compounds have already been documented to methylate mercuric ions in aqueous solution. Thus the study of transmethylation reactions opens up a new area of research that is essential in predicting the fate of organometals in the environment.     

Mercury analysis: a special example of species analysis

Summary Mercury species analysis requires the determination of numerous different compounds with very different behaviour regarding environment and toxicity. For these differing species several new and more sensitive analytical methods have been developed and tested. Mercury species cannot be detected directly in most cases, and are normally derivatized by different agents and determined by different detector systems. In a new HPLC method with photometric detection more than 10 different organomercurials could be analysed as their thio-ethanol complexes. By alkylation of mercury compounds they can be separated by GC and analysed with an AAS or AFS as detector. Volatile organic species of Hg can be separated on Carbotrap^®, where Hg⁰ is not adsorbed, and analysed thereafter. With atomic fluorescence the detection limit for Hg⁰ measurement is improved significantly when compared with the widely used atomic absorption method. Results obtained with this new method are shown and discussed. Future developments for species analysis are outlined; not only to analyse the covalent metal — carbon/oxygen compounds — primary species-analysis — but also compounds with ionic or complex bonding: secondary species-analysis. With these developments, prediction of species behaviour in the environment, including toxicity assessment and decontamination proposals, should be made possible.     

Speciation of ionic alkyllead in grass and tree leaves

A preliminary study aimed at outlining the potential of the extraction/derivatization/gas chromatography-atomic absorption spectrometry methodology for the species-specific determination of ionic organolead compounds in grass and tree leaves is described. A pretreatment procedure based on leaching the species from the matrix using tetramethylammonium hydroxide appeared to be efficient. In grass, concentrations up to 100 ng Pb g^-1 were detected; a reliable differentiation between the amount taken up and the amount superficially adsorbed could not yet be achieved.     

Ionic alkyl-lead,tetra-alkyl-lead and total lead in fish from the Great Lakes

Fillets from a variety of fish species collected from Lakes Ontario, Superior and Erie, Canada, were examined for ionic alkyl-lead, tetra-alkyl-lead and total lead compounds. Diphenylthiocarbazone (dithizone)-derivatized extracts were collected at pH 8 and 9 for ionic alkyl-leads from enzymatically hydrolyzed samples. Butylated derivatives were formed prior to analysis by gas chromatography-atomic absorption spectrometry (GC AA). Tetra-alkyl-lead was extracted from the hydrolyzates with hexane. Most of the fillets contained low (<0.08–2 ng g^?1) levels of trimethyl-lead. Several samples contained triethyl-lead or tetraethyl-lead. Dimethyl-lead, diethyl-lead and tetramethyl-lead were detected by GC MS but were below the GC AA method detection limit of 0.06 ng g^?1, 0.09 ng g^?1 and 0.2 ng g^?1 respectively. Total lead levels were between <1.8 and 96.7 ng g^?1.     

Amperometric titrations of organolead and organotin ions

Mixtures of R₂Sn²⁺ and R₃Sn⁺ compounds can be analysed by titrating their total amount potentiometrically with alkali, and then determining R₂Sn²⁺ in another aliquot by amperometric titration with standard 8-hydroxyquinoline solution. In mixtures of R₂Pb²⁺ and R₃Pb⁺ compounds, dialkyllead ion can be titrated amperometrically with ferrocyanide solution and trialkyllead ions with tetraphenylboron solution. A potentiometric method is described for the determination of small amounts of lead chloride in the presence of any alkyllead chloride.     

GC FPD method for the simultaneous speciation of butyltin and phenyltin compounds in waters

A method is described for the simultaneous determination of nanogram amounts of mono-, di- and tri-butyltin compounds in water. The procedure is based on the conversion of tin compounds to volatile species by Grignard pentylation and analysis using GC with flame photometric detection (GC FPD). The ionic compounds are extracted from diluted acidified (HBr) aqueous solutions by using a pentane-tropolone solution. The extracted organotin compounds are pentylated by a Grignard reagent and purified on a Fluorisil column before analysis by GC FPD. The detection limits are 20 ng dm^?3 for butyltin compounds and 50 ng dm^?3 for phenyltin compounds. Recoveries from spiking experiments in tap-water and natural seawater matrices, in which no organotin compounds were detected, were greater than 90% for most of the alkyltin compounds.     

Organic lead compounds in vehicle exhaust

Species-specific measurements of the five tetraalkyllead compounds used in gasoline and their intermediate decomposition products, the tri- and di-alkyllead species, have been made in vehicle exhaust fumes. Under normal engine running conditions 0.3–3% of the lead emitted in exhaust is as an organic compound, but cold, choked engines emit proportionally much larger amounts of alkyllead. Alkyllead is emitted in both the gas and the aerosol phases.     

Separation and identification of organic and organometallic compounds by use of a liquid chromatography-particle beam-glow discharge mass spectrometry combination

Evaluation of the particle beam glow discharge mass spectrometry (PB-GDMS) system as a detector for liquid chromatography (LC) is described for the analysis of polycyclic aromatic hydrocarbons, steroids, selenoamino acids, and alkyllead compounds. A particle beam interface is used to introduce analyte species from the LC into a glow discharge source for subsequent vaporization and ionization. Mass spectra display classic EI fragmentation patterns for the organic compounds, as well as elemental and molecular information for the organometallic compounds. Chromatographic separations display good temporal correlation between UV and PB-GDMS detection modes. Detection limits for Pb in lead nitrate, triethyllead, and triphenyllead fall in the sub-ppb (ng) range.     

Highly Efficient Nitric Oxide Capture by Azole‐Based Ionic Liquids through Multiple‐Site Absorption

A novel method for highly efficient nitric oxide absorption by azole‐based ionic liquid was reported. The NO absorption capacity reached up to 4.52 mol per mol ionic liquid and is significant higher than the capacity other traditional absorbents. Moreover, the absorption of NO by this ionic liquid was reversible. Through a combination of experimental absorption, quantum chemical calculation, NMR and FT‐IR spectroscopic investigation, the results indicated that such high capacity originated from multiple‐site interactions between NO and the anion through the formation of NONOate with the chemical formula R¹R²N?(NO^?)?N=O, where R¹ and R² are alkyl groups. We believe that this highly efficient and reversible NO absorption by an azole‐based ionic liquid paves a new way for gas capture and utilization.